FR2550191A1 - Novel cyclopropane carboxylic acid derivatives, a process for their preparation, and their use for controlling parasites. - Google Patents

Abstract

The invention relates to all possible isomers and to the isomer mixtures of the compounds of the formula I: in which the coupling of the cyclopropanoic acid has a 1R cis or 1R trans structure, X represents a halogen atom and R represents a hydrogen atom, a linear, branched or cyclic alkyl radical which is saturated or unsaturated and contained up to 12 carbon atoms, or the radical of an alcohol R-OH used in the synthesis of pyrethroids, where the geometry of the double bond on the carbon in the 3 position can have the E or Z structure. The invention also relates to a process for the preparation of the compounds of formula I. The invention equally relates to the application of the compounds of formula I in the control of parasites.

Description

 The present invention relates to novel cyclopropane carboxylic acid derivatives, process for their preparation and their application to pest control.

dans laquelle la copule acide cyclopropanique est de structure 1R cis ou 1R trans, X représente un atome d'halogene et R représente un atome d'hydrogéne, un radical alcoyle linéaire, ramifié ou cyclisé, saturé ou insaturé, renfermant jusqu'a 12 atomes de carbone ou le reste d'un alcool
R-OH utilisé dans la synthèse des pyréthrinoides, la géométrie de la double liaison portée par le carbone en 3 pouvant être de structure E ou Z.The subject of the invention is in all their possible isomeric forms as well as the mixtures of these isomers the compounds of formula (I)

in which the cyclopropanic acid copula is of 1R cis or 1R trans structure, X represents a halogen atom and R represents a hydrogen atom, a linear alkyl radical, branched or cyclized, saturated or unsaturated, containing up to 12 atoms carbon or the rest of an alcohol
R-OH used in the synthesis of pyrethroids, the geometry of the double bond carried by the carbon in 3 can be of structure E or Z.

 When R represents a linear, branched or cyclized, saturated or unsaturated alkyl radical, it is preferably methyl, ethyl, linear or branched propyl, linear or branched butyl, linear or branched pentyl, linear or branched hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-propenyl, 1-butynyl, 1,3-butediyl, 1pentenyl, 1-cyclobutynyl, 1-cyclopentadienyl, 1-cyclohexenyl.

dans lequel 5 représente un atome d'hydrogène ou de fluor et x représente
un atome de fluor, de chlore ou de broine

When R represents the residue of an alcohol used in the synthesis of pyrethroids, it is preferably the radical chosen from the group of the following radicals
A - the radicals -CH-Ardans which Z represents an atom
hydrogen, an ethynyl, methyl or cyano radical and Ar represents a radical

in which 5 represents a hydrogen or fluorine atom and x represents
a fluorine, chlorine or broine atom

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<tb> B <SEP> - <SEP> the radical <SEP>
<Tb>
C - the radical

formule dans laquelle Y2 représente un atome d'hydrogène, un atome de fluor, de chlore ou de brome, un groupement -C-N ou un groupement -Cr CH, Y3, Y4, Y5 identiques ou différents, représentent un atome d'hydrogène, un atome de fluor, de chlore ou de brome, un radical alcoyle linéaire, ramifié ou cyclique, renfermant de 1 a 8 atomes de carbone, éventuellement substitué par un ou plusieurs groupements fonctionnels, identiques ou différents, un radical alcényle comportant de 2 à 8 atomes de carbone ou un radical alcynyle comportant de 2 a 8 atomes de carbone, les radicaux Y3, Y4 et Y5 peuvent former les cycles entre eux deux a deux.D - and the radicals

formula in which Y2 represents a hydrogen atom, a fluorine, chlorine or bromine atom, a group -CN or a group -Cr CH, Y3, Y4, Y5 identical or different, represent a hydrogen atom, a fluorine, chlorine or bromine atom, a linear, branched or cyclic alkyl radical containing 1 to 8 carbon atoms, optionally substituted by one or more functional groups, which may be identical or different, an alkenyl radical containing from 2 to 8 atoms of carbon or an alkynyl radical having from 2 to 8 carbon atoms, the radicals Y3, Y4 and Y5 can form the rings between them two by two.

 The term "halogen atom" means fluorine, chlorine or bromine atoms, but the subject of the invention is particularly those compounds of formula (I) in which X represents a fluorine atom.

 The subject of the invention is especially those compounds of formula (I) for which the geometry of the double bond borne by the carbon at 3 of the cyclopropane is of structure Z.

Among the compounds of the invention, mention may be made especially of the compounds for which R represents a radical -CH-Ar, in which ZZ represents a hydrogen atom, a radical-C -CH, CH3 or a radical -C- -NOT
and Ar represents a radical selected from the group of radicals - C5H5 - C6F5

<tb> with <SEP> B = H <SEP> or <SEP> F
<tb><SEP> X = F, <SE> Cl, <SE> Br
in which B represents a hydrogen or fluorine atom and X represents a fluorine, chlorine or bromine atom and in particular the compounds for which Ar represents an X-cyano metaphenoxy benzyl radical such as 1R cis 2.2 or (S) -cyano metaphenoxybenzyl dimethyl 3 / z E 2-fluoro-2-cyano ethenyl / cyclopropane carboxylate or the corresponding Z isomer.

 The compounds of formula (I) have interesting properties which allow their use in the fight against pests, which may be, for example, the control of plant pests, parasites of premises and parasites of warm-blooded animals. Thus, the products of the invention can be used to control pest, nematode and parasitic mites of plants and animals.

 The invention therefore also relates to the application of the compounds of formula (I) as defined above to the control of plant pests, parasites of premises and parasites of warm-blooded animals.

 The products of formula (I) can be used in particular for controlling insects in the agricultural field, for example to combat aphids, lepidopteran larvae and coleopterans. They are used at doses of between 10 g and 300 g of active ingredient per hectare.

The products of formula (I) can also be used to control insects in the premises, in particular to fight against flies, mosquitoes and cockroaches.
The products of formula (I) may also be used to control plant-parasitic mites and nematodes.

 The compounds of formula (I) can still be used to fight against parasitic mites of animals, for example to fight against ticks and in particular ticks of the species Boophilus, those of the species Hyalomnia, those of the species Amblyomnia and those of the species Rhipicephalus or to fight against all kinds of scabies including sarcoptic mange, psoroptic mange and chorioptic mange. They can also be used against lice and helminths.

 The subject of the invention is therefore also compositions intended for combating plant pests, premises parasites and parasites of warm-blooded animals, characterized in that they contain as active principle at least one of the products of formula General (I).

 The invention particularly relates to the insecticidal compositions containing as active ingredient at least one of the products of general formula (I).

Among the particularly insecticidal compositions of the invention, mention may be made especially of compositions containing the compounds
described in the examples and in particular (S) d-cyano metaphenoxy (1R cis) 2,2-dimethyl 3 / (SE) 2-fluoro-2-cyano ethenyl / cyclopropane carboxylate
benzyl.

 These compositions are prepared according to the usual processes of the agrochemical industry. They may be optionally added with one or more other pesticidal agents. These compositions may be in the form of powders, granules, suspensions, emulsions, solutions, aerosol solutions, combustible strips, baits or other preparations conventionally used for the use of such compounds.

 In addition to the active ingredient, these compositions contain, in general, a vehicle and / or a nonionic surfactant, ensuring, in addition, a uniform dispersion of the constitutive substances of the mixture. The vehicle used can be a liquid, such as batten, alcohol, hydrocarbons or other organic solvents, a mineral oil, animal or vegetable, a powder such as talc, clays, silicates, kieselguhr or a solid fuel .

 The insecticidal compositions according to the invention preferably contain from 0.005 to 10% by weight of active material.

 According to an advantageous procedure, for use in the premises, the compositions according to the invention are used in the form of fumigant compositions.

 The compositions according to the invention can then be advantageously constituted, for the non-active part, of a combustible coil, or a non-combustible fibrous susbtrate. In the latter case, the fumigant obtained after incorporation of the active ingredient is placed on a heating apparatus.

 In the case where an insecticidal coil is used, the inert support may be. for example, composed of pyrethrum marc, Tabu powder (or Machilus Thumbergii leaf powder, pyrethrum stem powder, cedar leaf powder, wood powder (such as pine sawdust) starch and hull powder). coconut.

 The dose of active ingredient can then be, for example, 0.03 to 1 by weight.

 In the case where a noncombustible fibrous support is used, the dose of active material can then be, for example, 0.03 to 25% by weight.

 The compositions according to the invention for use in the premises can also be obtained by preparing a sprayable oil based on the active ingredient, this oil soaking the wick of a lamp and then being subjected to combustion.

 The concentration of the active ingredient incorporated in the oil is preferably from 0.03 to 25% by weight.

 The acaricide and nematicide compositions may be in particular in the form of powder, granules, suspensions, emulsions, solutions.

 The acaricide and nematicide compositions may be optionally added with one or more other pesticidal agents.

 For the acaricide use, wettable powders, for foliar spraying, containing from 1 to 80% of active ingredient or foliar sprays containing from 1 to 500 g / l of active ingredient are preferably used. It is also possible to use foliar powders containing 0.05 to 3% of active ingredient.

 For the nematicide use, it is preferable to use soil treatment liquids containing from 300 to 500 g / l of active ingredient.

 The acaricide and nematicide compounds according to the invention are preferably used at doses of between 1 and 100 g of active ingredient per hectare.

 The invention therefore also relates to the acaricide compositions containing as active ingredient at least one of the products of general formula (i) as well as the nematicidal compositions containing as active principle at least one of the defined products of general formula ( I).

 The invention also relates to the acaricide compositions containing as active ingredient at least one of the compounds of general formula (I), characterized in that they are used in the fight against parasites of warm-blooded animals, in particular against ticks and scabies.

 When it comes to combating animal parasites, the compositions may be used in the form of a spray, a bath, or according to the "for-on" method.

 When using the method for-one, it is preferable to use solutions containing 0.5 to 4 g of active ingredient per 100 cm3 of solution.

When it comes to controlling animal parasitic mites, it is possible to incorporate the products of the invention into food compositions in combination with a nutritive mixture suitable for animal feed. The nutrient mixture may vary depending on the animal species; it may contain cereals, sugars and grains of soybean meal, peanut meal and sunflower meal, meal of animal origin, for example fish meal, amino acids from
synthesis, mineral salts, vitamins and antioxidants.

The invention thus also relates to the compositions
for animal feed containing as active ingredient at least one of the products of general formula (t).

 The invention also relates to combinations endowed with insecticidal, acaricidal or nematic activity, characterized in that they contain as active ingredient, on the one hand at least one of the compounds of general formula (I) and of on the other hand, at least one of the pyrethrinol esters selected from the group consisting of esters of allethrolones, 3,4,5,6-tetrahydrophthalimido-methyl alcohol, 5-benzyl-3-furyl methyl alcohol, benzyl 3-phenoxy alcohol and 3-phenoxy benzyl alcohol-cyano chrysanthemic acids, by the alcohol esters 5-benzyl 3-furyl methyl 2,2-dimethyl-3- (2-oxo-3-tetrahydrothiophenylidene methyl) 1-carboxylic cyclopropane, with the esters of 3-phenoxybenzyl alcohol and 3-phenoxybenzyl alcohols of 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylic acids, with the esters of alcohols o (-cyano 3-phenoxy benzyl acids 2,2-dimethyl 3 (2,2-dibromovinyl) cyclopropan carboxylic esters, by the esters of 3-phenoxy benzyl alcohol of 2-parachlorophenyl 2-isopropyl acetic acids, by esters of allethrolones, 3,4,5,6-tetrahydrophthalimido methyl alcohol, 5-benzyl alcohol 3 methyl-benzyl alcohol, 3-phenoxy benzyl alcohol and o-cyano-3-phenoxy benzyl alcohols 2,2dimethyl 3- (1,2-2,2-tetrahaloethyl) cyclopropane 1-carboxylic acids in which "halo" represents a fluorine, chlorine or bromine atom, it being understood that the acidic copula and alcohols of the pyrethrinoid esters above may exist in all their possible stereoisomeric forms.

The subject of the invention is the insecticidal compositions defined above, characterized in that they also contain a pyrethroid synergist.
As conventional synergists used in such cases, there may be mentioned 1- (2,5,8-trioxadodecyl) 9-propyl 4,5-methylene dioxy benzene (or piperonyl butoxide) or N- (2-ethyl heptyl) bicyclo / 2,2-1 / 5-heptene 2,3 di carboximi of, or piperonyl-bis-2- (2n-butoxyethoxy) ethyl acetal (or tropital).

dans laquelle R conserve la même signification que précédemment å l'action d'un composé de formule (III)

dans laquelle X conserve la même signification que précédemment pour obtenir un composé de formule (I) correspondant que l'on soumet, si désiré, à l'action d'un agent d'estérification si R représente un atome d'hydrogène, ou que l'on soumet, si désiré, à l'action d'un agent de clivage de la fonction ester, puis, si désiré, à l'action d'un agent d'estérification.The subject of the invention is also a process for the preparation of the compounds of formula (I) as defined above, characterized in that, according to the Wittig reaction, a compound of formula (II) is subjected

in which R retains the same meaning as above with the action of a compound of formula (III)

in which X has the same meaning as above to obtain a corresponding compound of formula (I) which is subjected, if desired, to the action of an esterifying agent if R represents a hydrogen atom, or if desired, the cleavage agent is subjected to the ester function and, if desired, to the action of an esterification agent.

 The compounds of formula (II) and formula (III) are known products.

 The products of formula (III) can be prepared according to the method described in Helv. Chem. Acta. Vol. 60 (1977) p. 585.

The Wittig reaction generally used to prepare the products of formula (I) provides compounds of formula (I) whose geometry is
E + Z.

 The isomers at the double bond level can be separated, if desired, by physical methods such as chromatography, or at the level of the acids, or at the level of the alkyl esters, or at the level of the final esters.

 The cleavage agent of the CO2P group is preferably the heat used with an acid hydrolysis agent. As acidic hydrolysis agent, p-toluenesulphonic acid may be used.

 Esterification can be carried out in the presence of a tertiary base, such as pyridine. This esterification can be carried out advantageously in the presence of a mixture of pyridine, dicyclohexyl carbodiimide and 4-dimethylaminopyridine or pyridine.

 It goes without saying that the Wittig reaction, the cleavages of the ester functions, the esterification are reactions well known to those skilled in the art and need not be detailed here.

 The following examples illustrate the invention without limiting it.

EXAMPLE 1: 1 R cis 2,2-dimethyl 3 / (E + Z) 2-bromo-2-cyanoethenyl / -cyclopropanecarboxylic acid.

 3.5 g of bromo cyano methylene triphenyl phosphorane, 30 cm 3 of tetrahydrofuran and 4 cm 3 of dimethylformamide are mixed under an inert atmosphere. 1.39 of the 1 R cis 2,2-dimethyl dihydroxy methyl cyclopropane carboxylic acid lactone and 10 μl of tetrahydrofuran are added to the resulting solution. It is kept at room temperature for 16 hours and is evaporated to dryness. 5.8 g of an oily residue are obtained, which is chromatographed on silica, eluting with hexane, ethyl acetate (7.3) at 1% concentration. 'acetic acid . The mixture of isomers #E etaZ (F = 132 C) is obtained.

EXAMPLE 2: 1R cis 2,2-dimethyl-3 - [(E) 2-bromo [2-cyanoethylene] cyclopropane carboxylate of (S) -α-cyano-3-phenoxybenzyl and corresponding isomers.

30 mg of dimethylaminopyridine at 0 ° C. are added in 10 cm 3 of a solution containing 1.4 g of 1R cis-2,2-dimethyl-3 / (E + Z) 2-bromo-2-cyanoethenyl cyclopropane carboxylic acid and 1.4 g g of alcohol (S) -cyano
3-phenoxybenzyl. Dicyclohexylcarbodiimide and 5 cm 3 of methylene chloride are then added. The reaction mixture is allowed to return to 20 ° C. and stirred for 3 hours. The formed urea is filtered off, rinsed and the filtrate is evaporated to dryness to obtain 3.7 g of product, which is chromatographed on silica eluting with benzene. 1.3 g of # E isomer is obtained ( F = 600C) and on the other hand, 750 mg of Z # isomer (F = 64 C).

EXAMPLE 3: 1r cis 2,2-dimethyl 3 / (Z! Z) 2-fluoro-2-cyano ethenyl / cyclopropane carboxylate and terbutyl isomer bE.

A mixture containing 15 g of phenyl bromo-fluoro cyano methyl mercury and 180 cm 3 of xylene is stirred under reflux for 1 hour.
8 g of triphenylphosphine and 5.25 g
1R, cis 2,2-dimethyl-3-formyl cyclopropane tetbutyl carboxylate.

 It is ice-cold, filtered and the filtrate is brought to dryness. 20 g of a product are obtained which are chromatographed on silica eluting with pure benzene.

3 g of #E isomer (rf = 0.4-1.3 g of #z isomer (rf = 0.33)) are obtained.

Preparation of phenyl bromo fluoro cyano methyl mercury used at the beginning of the example.

a) Bromo fluoroacetamide
Concentrated ammonia (79 g) of ethyl bromofluoroacetate was added with concentrated stirring at +5 ° C. Stirring and temperature were continued for a further 30 minutes, evaporated to dryness and the residue distilled to give 53.6 g. expected product eb / 0,1 = 82-84 C.

(b) Bromo fluoroacetonitrile
92 g of phosphoric anhydride are added to 183 g of bromofluoroacetamide obtained as previously heated sufficiently to mix, and then the mixture is gradually heated to 200 ° C. (outside) and 87 g of expected crude product are distilled between 55 ° and 80 ° C.

c) Phenyl bromo fluoro cyano methyl mercury
15.65 g of mercuric phenyl chloride are cooled down to -50 ° C. in 100 cm 3 of tetrahydrofuran, 10.6 g of fluoro bromoacetonitrile, obtained as above, are added, then, again at -50 ° C., with stirring, a suspension containing 7.85 g of potassium tert-butylate, 50 cm3 of tetrahydrofuran and 6.6 cc of terbutyl alcohol.

 After 30 minutes, the reaction mixture is poured into ice water containing 6 cm3 of concentrated hydrochloric acid and extracted with chloroform.

The organic phase is dried and concentrated to dryness. The residue is taken up in a chloroform hexane (1/1) mixture, the insoluble material is filtered off, ice, filtered and 9.3 g of expected product are obtained (mp 130-132 ° C.).

 EXAMPLE 4 1-cis cis 2,2-dimethyl-3 ((Z) 2-cyano-2-fluoro ethenyl / cyclopropane carboxylic acid.

1.3 g of 1R cis-2,2-dimethyl-3- (2-fluoro-2-cyano-ethenyl-cyclopropanecarboxyl carboxylate, 13 cm.sup.3 of methylbenzene and 130 mg of para-toluenesulphonic acid are added at 120.degree.-130.degree. the reaction mixture is stirred for 15 minutes after the start of refluxing The reaction mixture is cooled to 20 ° C., washed with water and dried over sodium sulfate.
soda toluene solution, filter and bring it to dry under pressure
scaled down. 1 g of desired product is obtained.

 EXAMPLE 5 1R cis 2,2-dimethyl-3 - [(6E) 2-cyano-2-fluoro-ethenyl] cyclopropane carboxylic acid

 By operating as in Example 4, starting from the 1R cis 2,2-dimethyl 3 / (# E) 2-fluoro-2-cyano ethenyl / cyclopropane carboxylate terbutyl, the desired product is obtained.

EXAMPLE 6 1R cis 2,2-dimethyl 3 / (Z) 2-fluoro-2-cyano ethenyl / cyclopropane carboxylate (S) -α-cyano-3-phenoxybentyl.

 30 mg of dimethylaminopyridine are added at 5 ° C. to a solution containing 1 g of 1R cis-2,2-dimethyl-3 ((2 Z) 2-fluoro-2-cyanoethenyl / cyclopropane carboxylic acid, 6 cm 3 of methylene chloride and 1 g. 2 g of (S) -alpha-3-phenoxybenzyl alcohol. 1.1 g of dicyclohexylcarbodiimide and 8 cm3 of methylene chloride are then added. The reaction mixture is allowed to return to 20 ° C. and the mixture is stirred for 2 hours. 0.5 cm3 of acetic acid and 0.5 cm3 of ethanol are then added. The urea formed is then filtered off, rinsed with a little methylene chloride and the filtrate is brought to dryness. 2.8 g of product are obtained which is chromatographed on silica eluting with a mixture of methylene chloride and hexane ( 8-2). 1.5 g of the crude desired product are obtained. After recrystallization from refluxing isopropanol, 1.3 g of the desired product, melting at 90 ° C., are obtained.

EXAMPLE 7: 1 R cis 2,2-dimethyl 3 / (E + Z) 2-chloro-2-cyanoethenyl / cyclopropane carboxylic acid.

 By operating as in Example 1, starting from chloro cyanomethyl triphenyl phosphorane, the desired product (F <50 ° C.) is obtained.

EXAMPLE 8: 1R cis 2,2-dimethyl 3 / (e) 2-chloro-2-cyano ethenyl / cyclopropane carboxylate (S) -cyano-3-phenoxybenzyl and isomer # z corresponding.

 Operating as in Example 2, starting from the acid prepared in Example 7, the first isomer #E (F = 66 C) was obtained on the other hand, the isomer #z (F = 630C).

EXAMPLE 9: 1R trans 2,2-dimethyl 3 / (X E) 2-cyano-2-fluoro ethenyl / cyclopropane carboxylate (S) 4 -cyano metaphenoxybenzyl and corresponding ## isomer.

 A mixture containing 10 g of 1R trans 2,2-dimethyl-3-formyl cyclopropane carboxylic acid, 8 g of triphenylphosphine, 180 cm 3 of xylene and 15 g of phenylbromo-cyano-fluoro-methyl-mercury is refluxed under agitation for 2 hours. . It is ice-cold, drained and the filtrate is brought to dryness. 24 g of an oil are obtained which are chromatographed on silica eluting with toluene. After several "HPLCs", 835 mg of isomer Z (alpha = 17 + 1 5 -c = 1% in CHCl 3) and 1.8 g of #E isomer (D = -21 + 205 c = 0) are separated off. , 5% in CHCl3).

EXAMPLES 10 to 22
By operating as above, the following products having the following formula (I) were obtained:

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<tb><SEP> 11 <SEP> Br <SEP> E <SEP> 1Rcis
<tb><SEP> 12 <SEP> Br <SEP> E <SEP> 3 <SEP> lacis
<tb><SEP> Z <SEP> Br
<tb><SEP> 13 <SEP>'<SEP> E
<tb><SEP> ci '
<tb><SEP> 14 <SEP> El <SEP> El <SEP> El <SEP> M
<tb><SEP> 15 <SEP> -cd /, 10
<tb><SEP> 16 <SEP> C1 <SEP> 11 <SEP> 1 <SEP> ltrans
<tb><SEP> Ct.
<Tb>

<SEP> 17 <SEP>"<SEP> i <SEP> E '
<Tb>

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<tb><SEP> 18 <SEP> C1 <SEP> E <SEP> Iscis
<tb><SEP>'E<SEP> Z <SEP>"
<tb><SEP> 19 <SEP> Cl <SEP> 3
<tb><SEP> E <SEP> E, <SEP> -r <SEP>
<tb><SEP> L
<tb><SEP> 20 <SEP>., <SEP> E + Z <SEP>"
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<tb><SEP> 21 <SEP> I <SEP> It <SEP> ll <SEP> M
<tb><SEP> 22 <SEP> F <SEP> Z <SEP> 1Retrans
<Tb>
EXAMPLE 23 Preparation of a soluble concentrate

A homogeneous product mixture of Example 6 was carried out... 0.25 g - Piperonyl butoxide ... .................. 1.00 g - tween 80 ......................... ............. 0.25 g - topanol A .............................. ....... 0,1 g - water ..................................... ...... 98.4 g
EXAMPLE 24 Preparation of an Emulsifiable Concentrate

product of example 10 ............................. 0.015 g - piperonyl butoxide ........ ..................... 0.5 g - topanol A ...................... .................... 0.1 g - tween 80 ....................... ..................... 3.5 g - xylene ....................... ...................... 95.885 g
Study of the lethal effect on larvae of Spodoptera Littoralis.

The tests are carried out by topical application of a toxic acetone solution using the Arnold micro-manipulator on the dorsal thorax of the caterpillars.The LD50 of the product is determined using
Larvae per dose of test product The larvae used are larvae of the fourth instar larvae, that is to say, about 10 days old in culture on artificial medium (Poitout medium) at 24 ° C. and 55 relative humidity. . After treatment, the individuals are observed on artificial nutrient medium.

 Mortality control is performed 48 hours after treatment.

 The experimental results obtained for the products of Examples 2, 6 and 8 are between 0.48 and 4.8 ng per insect.

Study of the slaughter effect on houseflies.

 Test insects are female house flies aged 4-5 days. It is carried out by direct spraying at a concentration of 0.25 g / l in a Kearns and March chamber using as solvent a mixture of acetone (5%) and Isopar L (petroleum solvent) (amount of solvent used 2 ml in one second). 50 insects are used per treatment. The slaughter checks are carried out every minute for up to 10 minutes, then at 15 minutes and the KT 50 is determined by the usual methods.

 the experimental results obtained for the products of Examples 2, 6 and 8 expressed in KT 50 in minutes are between 1.8 and 3.6 minutes.

Claims (14)

 1) In all their possible isomeric forms as well as the mixtures of these isomers the compounds of formula (I)

 wherein the cyclopropane acid copula is of 1R cis or 1R structure  trans, X represents a halogen atom and R represents an atom  of hydrogen, a linear, branched or cyclized alkyl radical, saturated or  unsaturated, containing up to 12 carbon atoms or the rest of an alcohol  R-OH used in the synthesis of pyrethrinids, the geometry of the double  bond borne by the carbon in 3 which can be of structure E or Z.  2) The compounds of formula (I) as defined in claim 1  wherein X represents a fluorine atom.  3) The compounds of formula (I) as defined in any one of  claims 1 or 2 for which the geometry of the double bond  carried by the carbon in 3 of the cyclopropane is of structure Z.  4) The compounds of formula (I) as defined in any one of  claims 1 or 3 for which R represents a radical -CH-Ardans 2  Z represents a hydrogen atom, a radical CECH, CH3, a radical -CEM and Ar represents a radical chosen from the group of radicals  - C6H5 C6F5

 with fn = H or F  X = F, C1, Br wherein B represents a hydrogen or fluorine atom and X represents a fluorine, chlorine or bromine atom.  5) The compounds of formula (I) as defined in claim 4  in which Ar represents a -cyano metaphenoxybenzyl radical.  6) The compounds of formula (I) as defined in claim 1  whose names follow  1R cis 2,2-dimethyl 3 / (S E) 2-fluoro-2-cyanoethenyl / cyclopropane  (S) o (-cyano metaphenoxybenzyl) carboxylate and the nz isomer  corresponding.  7) Application of the compounds of formula (I) as defined in one  any of claims 1 to 6 for the control of pests of  plants, parasites of premises and parasites of blood animals  hot.  (b) Compositions for the control of pests of  plant viruses, parasites of premises and parasites of warm-blooded animals, characterized in that they contain as active ingredient at least one of the products defined in any one of claims 1 to 6.  9) The insecticidal compositions containing as active principle at least one of the products defined in any one of claims 1 to 6  10) The acaricide compositions containing as active principle at least one of the products defined in any one of claims 1 to  6  11) The nematicidal compositions containing as active ingredient the  least one of the products defined in any one of claims 1 to 6.  12) The acaricide compositions containing as active ingredient at least one of the products defined in any one of claims 1 to 6, characterized in that they are used in the fight against  parasites of warm-blooded animals, particularly ticks and  gales.  13) Compositions intended for animal feed containing  as active ingredient at least one of the products defined in any one of  Claims 1 to 6.  14) Associations with insecticidal, acaricidal or  nematicide, characterized in that they contain as active ingredient,  on the one hand at least one of the compounds of general formula () and other  at least one of the pyrethrinol esters selected from the group  consisting of esters of allethrolones, 3,4,5,6-tetrahydro-  methyl phthalimido, 5-benzyl 3-furyl methyl alcohol, alcohol 3  benzyl phenoxy and benzoic alcohols 3-phenoxy benzyl acids  chrysanthemics, by the 5-benzyl-3-furyl methyl alcohol esters of 2,2-dimethyl-3- (2-oxo-3-tetrahydrothiophenylidene methyl) cyclopropane 1-carboxylic acids, by the 3-phenoxy benzyl alcohol esters and 3-phenoxybenzyl alcohols of 2,2-dimethyl-3- (2,2-dichlorovinyl) cyclopropane-1-carboxylic acids, by the esters of C (- cyano) 3-phenoxybenzyl alcohols of 2,2-dimethyl-3-acids - (2,2-dibroniovinyl) cyclopropane 1-carboxylic acid, by the esters of alcohol 3-phenoxy benzyl parachlorophenyl 2-isopropyl acetic, by the esters of allethrolones, alcohol 3,4,5,6-tetrahydrophthalimide methyl, alcohol-5-benzyl-3-furyl methyl, 3-phenoxy benzyl alcohol and alcohols (-cyano-3-phenoxy benzyl) 2,2-dimethyl-3- (1,2-2,2- 1-carboxylic tetrahaloethyl) cyclopropane in which "halo" represents a fluorine, chlorine or bromine atom, it being understood that the acidic copula and alcohols of the pyrethrinol esters above can exist in all their possible stereoisomeric forms.  15) The compositions according to any one of claims 8 to 14 characterized in that they further contain a synergist pyrethrin noides.  16) Process for the preparation of the compounds of formula (I) as defined in any one of claims 1 to 6, characterized in that lton according to the Wittig reaction a compound of formula (II)

 in which R has the same meaning as in claim 1 to the action of a compound of formula (III)

 in which X has the same meaning as in claim 1 to obtain a corresponding compound of formula (I) which is subjected, if desired, to the action of an esterifying agent if P. represents an atom of hydrogen or that is subjected, if desired, to the action of a cleaving agent of the ester function, then, if desired, to the action of an esterification agent.